Nitraza esters



Unite 1 2,978,497 NTIIRAZA nsrnns Milton B. Frankel, Pasadena, and KarlKlager, Monrovia, 'Calif., assignors to Aerojet-General Corporation,Azusa, Califi, a corporation of Ohio No Drawing. Filed Aug. 22, 1955,Ser. No. 529,948

'22 Claims. (Cl. 260-482) wherein R is a hydrogen or alkyl radical, R isan alkyl or nitroalkyl radical and A and A are alkylene radicals.

These compounds are excellent plasticizers for nitropolymers, such asnitrocellulose or the polyurethane plastics disclosed in assigneescopending application Serial No. 422,649, filed April 12, 1954, nowabandoned. Commercial plasticizers used at the present time arenonexplosive and hence detract from the explosive power of thenitropolymers into which they are incorporated. The compounds of thisinvention, however, are not only plasticizers but also exhibit highexplosive energy.

The nitropolymers can be polymerized in the presence of the nitrazaester or the nitraza ester can be blended into the nitropolymer afterpolymerization. The plasticizer is incorporated into the nitropolymer inamounts of preferably from about 10% to about 40% by weight of thetotalmixture.

The nitraza esters of'this invention'are prepared by reacting a nitrazaacid or acid halide with an alcohol, in accordance with the generalreaction scheme set forth below:

wherein R is a hydrogen or alkyl radical, R is an alkyl or nitroalkylradical, A and A are alkylene radicals and X is a halogen or hydroxyradical. v

The reaction is preferably conducted in the presence of a Friedel-Craftscatalyst such as aluminum chloride, titanium tetrachloride, antimonypentachloride, boron trifluoride, ferric chloride, etc., due to theimproved yields obtained.

Either acids or acid halides can be employed as starting materials inthe practice of our invention, however, we prefer to use acid halidesdue to the superior yields and faster reaction rates obtained.

The acids and acid halides employed as, starting materials in thepractice of this inventoin are prepared by condensing an amino acid witha nitroalkanol followed by nitration of theamine group with nitric acid.The corresponding acid halides are prepared by halogenating the acidwith a conventional halogenation agent such as thionyl chloride. Theseprocedures are more fully disclosed in assig'nees copending applicationSerial No. 416,386, filed March 15, 1954, now abandoned.

- To more clearly illustrate this invention, the following examples arepresented. It is to be understood, how ever, that these examples arepresented merely as a means of illustration and are not intended tolimit the scope of the invention in any way.

States Patent 0 EXAMPLE I Preparation of methyl3,5,5-trinitro-3-aza-hexanoate 3,5,5-trinitro-3-aza-hexanoyl chloridewas dissolved in methanol and refluxed for one half hour. Upon cooling aquantitative yield of methyl 3,5,5-t1initro-3-aza-hexanoate precipitatedas white crystals, M.P. 80 C. Elemental analysis of the product was asfollows:

Calculated for C H N O Percent C, 27.07; percent H, 3.79; percent N,21.05. Found: Percent C, 27.59; percent H, 3.79; percent N, 20.95.

EXAMPLE II Preparation of2,2,Z-trinitroethyl-3,5,5-trinitro-3-azahexanoatetered, the solid waswashed with cold dilute hydrochloric acid, water, dried andrecrystallized from ethylene dichloride using charcoal to give 2.13 gm.(50.3%) of white crystals, M.P. 121-1215 C. Elemental analysis of the.

product was as follows:

Calculated for C H N O i Percent C, 20.25; percent H, 2.19; percent N,23.62. Found: Percent C, 20.37;

percent H, 2.09; percent N, 23.70.

In. the same manner as described in the above examples, other members ofthe disclosed class of esters can be prepared. For example, n-propyl4,7,7trinitro-4-.

aza-octanoate is prepared by reacting 4,7,7-trinitro-4-azaoctanoylchloride with n-propanol; 2-nitroethyl 3,5,5-trinitro-3-aza-pentanoateis prepared by reacting 3,5,5-trinitro-3-aza-pentanoyl chloride with2-nitroethanol; 2,2,- 4,4-tetranitrobutyl4,6,6-trinitro-4-aza-heptanoate is prepared by reacting 4,6,6trinitro-4-aza-heptanoyl chloride with 2,2,4,4-tetranitrobutanol;2,2-dinitropenty1 3,7,7-tri-' nitro-3-aza-decanoate is prepared byreacting 3,7,7-trinitro-3-aza-decanoyl chloride with2,2-dinitropentanol-l; and 2,2-dinitropropyl3,5,5-trinitro-3-aza-hexanoate is prepared by reacting3,5,5-trinitro-3-aza-hexanoyl chloride with 2,2-dinitropropanol.

Any member of the disclosed class of nitraza esters can be prepared byreacting an appropriate alcohol with a nitraza acid or acid halide inaccordance with the teachings of this invention.

This application is a continuation-in-part of our copending applicationSerial No. 416,382, filed March 15, 1954, now abandoned.

We claim:

1. As new compositions of matter, nitraza esters having the generalformula:

wherein R is aradical selected from the group consisting of hydrogen andlower alkyl radicals, R is a radical selected from the group consistingof lower alkyl and lower nitroalkyl radicals and A and A are loweralkylene radicals.

2. As new compositions of matter, nitraza esters having the generalformula:

'NO: No, 0."?

R( JA-I IA'0-0R' Patented Apr. 4, 1961 I 'wherein R is a lower-'alkylradicaL- R isv a lower nitr'o- {alkyl-I radicaland A and A' are loweralkylene radicals. I

' '3. As new compositionsof: matter, nitraza esters ha'v I ing thegeneral formula:' I I I I I I I I I I I I I I I selected from the groupconsisting of lower alkyl and. I I i I lower I nitroalkyl radicals, Xis; a radical selected; {from I the group consisting of halogen andvhydroxy radicals- I I I I andA and A arelower. alkylene radioals 12. Themethod of claim 11 wherein :thereactionis; I. I

Noz Noz Q I H I I I I I I conducted in the presence of-a-FriedelCraftscatalyst. I I I I I I I I 1 I i i I I I 13; The method; f claim .11wherein the reaction is i I I I conducted in the presence-of aluminum:chloride. I I I I "wherein'a 'and'R are lower .alkyl radicals Iand AandA? 1 heme h d'o preparing nitrazfl esters h rms t e I I I are loweralkyleneradicals. I I genera}, mi e? I I I 4. As a new composition ofmatter, 2,2,2-trinitroethyl- I I I I I I I I Igig-airlines-aza-hexanoate- :havingthe structural; tf0r- L 1 I I I I I,-No N o NO: I f I I I i N d IN' I I I 19 which comprises reactmganalkanol with anacid halide CH: C.-CHzIN-CHr-C I In I I I I I I I I IIhavingtheIgenerali-omlulaz I I I N01 N01 N0, N02 0 1 I1 5, As'a'newcompositionofmatter, methy 3 t f I n- -'A-'N-A- II nitro-3-azahexanoatehaving the structural. torrtmlazv I I I I I I I I I I I I I I II I I II I I I I :;N0. .N 0 I I a I I I ,l 3 '1' OIIH wheremR and R arelowe ralkylradrcalsAandAfare.

. 'Q' 'f C'I' N' C I I I I 3 I lowe r alkylene radicals and X is ahalogen radical.

N0: I I I 15. The method of preparing nitraza' esters havingthe. I I I II 6. As' anew composition of matter, n-propyl; 4,7,7 -trie e s al Qrm lwI I I I itro-4-aza-octanoate having the structural. formula I I I I1;;0; N Oz I I I I I I IIIOI IIqOI II 3 I I ;gm. jm JsI-CHgCHFCOiCHzCHaCfii. i: i i i ii i IQ" rro'i I I I I I I I IIwhich-comprises. reacting .a'nitroalkanol: with. anacid I masts newcompositionof'matter,f2 nitroethyl; 3 ,5;5-I';.;i ha mgt ea s s formulwI I I I trinitro 3-azapentanoate having the structural-formula; I I I II No, 11ml I i I I I I I I I II llqOz -NIO2 I il) .A -A' -.XH(IJ-CHz-N-CH2-C- 0*+CH2CH2NQ1. I I I 1 I I I I I I I I I I I 'YYIZQI'NOIL I I I I I I I I I I II wherein'R is-aloweralkylradical, ,";is alowerznitro I 8.iAs a new composition.of'matter;.ZQAA-fifi fliiUOk: el it wtlax I ,I nm A'and. i t I bntyl 4,6,6-trinitro-4-azaheptanoate havingthe-structural 9W f a l i d s a. I I I I L I I t I I I .f m 1 :I,I I I III I 16. The 'method of prepa rmg' 2,2,2'-t,r1n1troethyl 3, 5, I f; I Ii i 3 I i I 4 trinitro-3aza-hexanoate which comprises reacting 3,5,5-

Y 7 f trinitro-3-aza-hexanoyl chloride with2,2,2-trinitroethanohGHr-CCHt-NCHflCHPC 0CHPG-OHF'CH I 17. The method of preparing methyl3,5,5-trinitro-3- NO: NO, NO; aza-hexanoate which comprises reacting3,5,5-trinitro-3- 9. As a new composition of matter, 2,2-dinitropentylaza'hexanoyl chlonde Wlth nlethaml- 3,7,7-trinitro-3-aza-decanoatehaving the structural for- The of prepalmg P q i mula: aza-octanoatewhich compnses reacting 4,7,7-tr1n1tro-4- aza-octanoyl chloride withn-propanol. Y I H Y 19. The method of preparing Z-nitroethyl3,5,5-trinitro- CH3OHaCHr-FCHztCHaCHrN-GHz-C-OCHz-C-CHnCHzCH:3-aza-pentanoate which comprises reacting 3,5,5-trinitro-3-aza-pentanoyl chloride with Z-nitroethanol.

20. The method of preparing 2,2,4,4-tetranitrobutyl 3 gl gg g igi if i52335 f ggg zi ggfiiggfi 2 g} 4,6,6-trinitro-4-aza-heptanoate whichcomprises reacting g 4,6,6trimtro-4-aza-heptanoyl chloride with2,2,4,4-tetramu nitrobutanol.

. Not H fil 21. The method of preparing 2,2-dinitropentyl 3,7,7- GH-dl-CH-N-OH,O-OOHz-G0Hz I trinitro-3-aza-decanoate which comprisesreacting 3,7,7- l 1m trinitro-3-aza-decanoyl chloride with2,2-dinitropenta- I nol-l.

11. The method of preparing mtraza esters-having the The method ofPreparing zIzdiniu-opmpyl 3I5I5 general formula Itrinitro-3-aza-hexanoate which comprises reacting 3,5,5- I 'Oa 1\|T02 3trinitro-S-aza-hexanoyl chloride with 2,2-dinitropropanol. R- N--A -OR EC References Cited in the file of this patent wherein R is a radicalselected from the group consisting of hydrogen and lower alkyl radicals,R is a radical UNITED STATES PATENTS 2,485,855 Bloomquist et a1. Oct.25, 1949 FOREIGN PATENTS 138,456 Sweden -Dec. 23, 1952 OTHER REFERENCESHolstead et al.: J. Chem. Soc. (London), 1952, pp. 1886-94.

1. AS NEW COMPOSITIONS OF MATTER, NITRAZA ESTERS HAVING THE GENERALFORMULA: